Chemical heating composition



Patented Feb. 13, 1951 CHEMICAL HEATING COMPOSITION- Maison G. deNavarre, Grosse Pointe Farms, Mich., and'William C. Grimn,.Ncwport,Del., assignors to Atlas Powder Company, Wilmington, Del., a corporationof'Delaware No Drawing. Application October 28, 1947, Serial No. 782,670

The present invention relates to chemical heating compositions.

An object of the invention is to provide. an improved heatingcomposition of the type employing an inorganic oxidizing agent and anorganic oxidizable material which undergo an exothermic chemicalreaction.

Another object is to provide an improved chemical heating compositionuseful in the machineless waving of hair.

The above and other objects will become ap- 8 Claims. (01. 132-363)parent in the course of the following description.

This invention relates to the type of chemical heat generation in whicha soluble oxidizing agent is enclosed in a water-permeable envelope andan aqueous solution of oxidizable material is brought into contact withthe oxidizing agent to produce an exothermic reaction. In themachineless permanent waving of hair, the envelope containing theoxidizing material is made of appropriate size and shape so that it canbe wrapped about a tress of hair formed into the desired shape on amandrel. The oxidizable solution is brought into contact with thisenvelope by means of an absorbent pad impregnated with the solution andsuitably shaped to engage the envelope. The envelope and pad are pressedtogether against the hair by means of a clamp in the conventionalmanner. The oxidizing material generally employed is potassiumpermanganate, although other soluble permanganates such as the sodiumand ammonium salts are useful, and other oxidizing agents such assoluble chlorates can be used. As oxidizable materials, the art hasgenerally employed glycerol, hexitols, some, of the sugars, and glycols.Difllculties have been experienced in using these oxidizable materialsby reason of their hygroscopicity which makes it difilcult to stabilizethe solutions as to water content. The water content is a criticalfactor in formulating these oxidizable solutions and substantialvariation from the desired composition results in failure of the heatingunit to produce the necessary degree of heating or results in theproduction of an undesirably high temperature during the reaction.Certain of the solid members of the class of materials usually employedcause a further difficulty due to their tendency to crystallize out ofthe solution, thus changing the composition in a way to reduce theefiectiveness of the unit to generate heat.

In accordance with the present invention, it has been found thatchemical heating units of the type described are improved with respectto stability and heat control by the use of a novel oxidizable solution.The oxidizable solution used according to the invention contains water,ethylene glycol, and a polyoxyethylene ether of a compound selected fromthe group consisting of hexitols, hexoses, and hexobioses, in which theether contains from 3 to 100 oxyethylene groups per molecule. Thepolyoxyethylene ethers of. this class are water-soluble,non-crystallizing materials which are much less hygroscopic than thematerials formerly used and have little or no tendency to attractadditional water to the solutions as they are prepared for use. Thesepolyoxyethylene ethers have been found to undergo an exothermic reactionwith soluble permanganates, although by themselves this reaction is notsufliclently vigorous to produce the necessary high temperature for hairwaving. The addition of ethylene glycol has been found to contribute tothe reaction in such a way that the desired temperature, C. or slightlyhigher, is readily attained. The combination of the ethylene glycol andthe polyoxyethylene ether in the oxidizable solution produces a reactionwith the soluble permanganate which causes the prompt attainment of thedesired high temperature and continues to generate heat at thistemperaturefor a period of several minutes. The ethylene glycol alonegives a characteristic rapid rise to a maximum temperature and rapidfalling off, whereas the combination of ethylene glycol andpolyoxyethylene ether shows a sustained rate of heat generation for amuch longer useful period.

The oxidizable solution used according to the invention can bedistributed in bulk form and the operator can dip a suitable absorbentpad into the solution and place it in contact with the permanganateenvelope at the time of use. Al-

ternatively, absorbent pads of suitable structurev can be impregnatedwith the solution and distributed in their moist condition ready foruse.

The polyoxyethylene ethers referred to are known compounds which arepreferably prepared by reacting the selected hexitol or sugar withethylene oxide under conditions of elevated temperature and pressure.Such compounds and methods of making them are described, for exconceptof the invention. The composition of Example 9 is the preferred productfor use in maa solution of the hexitol or sugar in water. The amount ofwater that'can be used is variable over a wide range, suitableproportions being from to about 50% water based on the totalcomposition. The water reacts with ethylene oxide under these conditionsto form glycols, principally the polyethylene glycols. The nature'of thecompositions produced depends on the relative proportions of the hexitolor sugar, water, and ethylene oxide. It is therefore to be understoodthat these products are complex mixtures of related materials whichdifierfrom one another principally in the number of oxyethylene groupscontained.

The polyoxyethylene ethers referred to can be made from any of thehexitols, the most important members being sorbitol, mannitol, anddulcitol, or any of the hexoses of which the most useful members areglucose and fructose, or any of the hexobioses of which the mostimportant are sucrose, lactose, and maltose. If desired, products can bemade from mixtures of any of these compounds.

Preferred oxidizable solutions are those which contain by weight from 70to 35% of the polyoxyethylene ether, from to 50% ethylene glycol andfrom 10 to 30% water, toa total of 100%. The examples illustrate severaltypical ratios within these ranges.

While the invention is particularly directed to compositions for use inthe machineless waving of hair, it will be appreciated that thesecompositions are also useful in other applications such as body warmersand food warmers. Certain of the compositions of the invention areparticularly well adapted to these other uses by reason of the fact thatthey produce their heat over a prolonged period of time.

The following table sets forth the composition in weight percent of anumber of oxidizable solutions that can be used in conjunction withpotassium permanganate to generate heat for use in chineless hair wavingbecause of the s with which the waving temperature is attained and thehigh total heat evolved.

It will be obvious that other ingredients can be added to thecompositions of the invention for various specific purposes. Thus,materials can be added to impart a pleasant odor to the vapors evolvedduring use. Coloring agents can likewise be added.

What is claimed is:

1. An oxidizable composition for use in heat generating reaction with awater-soluble oxidizing agent, comprising from 70 to by weight of atleast one polyoxyethylene ether of a compound selected from the groupconsisting of hexitols,'hexoses, and hexobioses, said ether containingfrom 3 to 100 oxyethylene groups per molecule, from 20*to 50% by weightethylene glycol, and from 10 to 30% by weight of water, to a total of100%.

2. An oxidizable composition for use in heat generating reaction with awater-soluble oxidizing agent, comprising from '70 to 35% by weight ofpolyoxyethylene ether of sorbitol containing from 3 to 100 oxyethylenegroups per molecule, from 20 to 50% by weight ethylene glycol. and from10 to 30% by weight water, to a total 0! 100%.

3. An oxidizable composition for use in' heat generating reaction with awater-soluble omdizing agent, comprising about 20% by weight water,about 40% ethylene glycol, and about 40% hair waving or for otherpurposes. These soluof the reaction product of 220 parts by weightethylene oxide with 100 parts by weight glucose and 50 parts by weightwater, said reaction product containing a polyoxyethylene ether ofglucose having from 3 to 100 oxyethylene groups per molecule. 4. Anoxidizable composition for use in heat generating reaction with'a watersoluble oxidizing agent, comprising from '70 to 35% by weight ofpolyoxyethylene ether of glucose containing from 3 to 100 oxyethylenegroups per molecule, from 20 to 50% by weight of ethylene glycol, andfrom 10 to 30% by weight of water, to a total of 100%.

5. A composition comprising (1) from to 35% by weight of apolyoxyethylene ether containing from 3 to owethylene groups permolecule of at least one member of the group Polyoxyethylene Ether PerCent Ethylene Glycol Per Cent Eth Per Cent er Water of waterPolyoxyethylene'cthcr produced by reacting 1138 of water Polyoxyethyleneether produced by reactin 2132 rtsb of water Same as Example 8Polyoxyethylene ether produced by reacting 440 of we Polyoxyethylenesorbitol with 3 oxyethylene groups per molecule. Polyoxyethylenesorhitol with 6 oxyethylene groups per molecule- Polyoxyethylene etherproduced by reactin 218 parts by weight of ethylene oxide with 100 partsof sorbito dissolved in 50 parts ts by weight of ethylene oxide with 100parts of sorbitol disso ved in 18 parts by weight of ethylene oxide with100 parts of sorbito disso ved in 18 parts by weight of ethylene oxidewith 100 parts of glucose dissolved in 60 parts ywc ht vedinlspia rts tsb weight in 25 pats Polyoxyethyleno ether produced by reacting 220 artsby weight of ethylene oxide with 100 parts of glucose disso ved in 50parts eeee aee set-ea Many variations of the compositions of theexamples can be made without departing from the consisting of hexitols,hexoses and hexobioses, together with the other reaction productsobtained when the said polyoxyethylene ether is prepared by the reactionof ethylene oxide with a solution composed 01' from to about 50% waterand from 95 to about 50% of said member; (2) from 20 to 50% by weight ofethylene glycol; and (3) from to 30% by weight of water, to a total of100%.

6. A composition as in claim 5 wherein the member 01 said group issorbitol.

7. A composition as in claim 5 wherein the member of said group isglucose.

8. In a heating device of the type described. for the machineless wavingof hair, the element which comprises an absorbent pad containing anoxidizable solution comprising from 70 to35% by weight of at least onepolyoxyethylene ether of a compound selected from the group consistingof hexitols, hexoses, and hexobioses, said ether having from 3 to 100oxyethylene groups per molecule, from to 50% ethylene glycol, and

5 from 10 to water.

The following references are of record in the file of this patent:

UNITED STATES PATENTS Number

8. IN A HEATING DEVICE OF THE TYPE DESCRIBED, FOR THE MACHINELESS WAVINGOF HAIR, THE ELEMENT WHICH COMPRISES AN ABSORBENT PAD CONTAINING ANOXIDIZABLE SOLUTION COMPRISING FROM 70 TO 35% BY WEIGHT OF AT LEAST ONEPOLYOXYETHYLENE ETHER OF A COMPOUND SELECTED FROM THE GROUP CONSISTINGOF HEXITOLS, HEXOSES, AND HEXOBIOSES, SAID ETHER HAVING FROM 3 TO 100OXYETHYLENE GROUPS PER MOLECULE, FROM 20 TO 50% ETHYLENE GLYCOL, ANDFROM 10 TO 30% WATER.